Azodyestuffs derived from 1:8-naphthalene dicarboxylic acid and process of making the same



Patented Apr. 24, 1928.

UNITED STATES 1,667,318 PATENT OFFICE.

MAX ISLER AND LUCAS VON MECHEL, OF BASEL, SWITZERLAND, ASSIGNORS TO THE FIRM: SOCIETY OF CHEMICAL INDUSTRY IN BASLE, OF BASEL, SWITZERLAND.

AZODYESTUFFS DERIVED FROM 1:8-NAIPHTHALENE DICARBOXYLIC ACID AND PROCESS OF MAKING THE SAME.

No Drawing. Application filed August 3, 1925, Serial No. 48,004, and. in Switzerland August 16, 1924.

This invention relates to new azodyestnfl's valuable for the production of fast tints on the fibre. It comprises the new products, the process of making the same, and the material dyed with the new dyestuffs.

It has been found that new dyestuffs may be obtained by converting 3-amino-1.8-naphthalcnesdicarboxylic acid into azodyestuffs. This may be done, either by combining it with diazo compounds, or by diazotizing said dicarl'ioxylic acid and coupling it with coupling con'iponents. There are thus obtained dyestuffs which are derived from 3- aminonaphthalene-l.8-dicarboxylic acid, the general formula of which is characterized by the presence of a LS-naphthalic acid complex (.0011 (,JUOU

not containing any hydroxyl groups. The new dyestuffs form yellow to brown and black powdels, dissolving in water with yellow to brown. violet and blue, in sulfuric acid with greenish-yellow, orange to brown, bluish-red and greenish-blue coloration and dyeing wool inan acid bath yellow to brown, violet and grayish-blue tints. ()wing to the presence of the two carboxylic groups all these dyestufi's are more or less pronounced mordant dyestuffs.

- Ezvample J.

- ish-brown powder, dissolving in water with yellowish-red, in concentrated sulfuric acid with brown coloration. It dyes wool in an acid bath brick-red tints fast to washing, changing very little and becoming fast, es pecially fast to potting, by treatment with chromium, When printed in presence of chromium mordants it yields orange tints.

corresponds most probably'with the following formula:

COONa 000m If instead of sulfanilic acid other amino-- sulfonic acids are employed, as for instance tolnidine-, chloroauiline-, aminophenol-ether-, naphthylamine-sulfonic acids, etc., analogous dyestuffs are obtained. The corresponding unsulfonated amines as well as the aminocarboxylic acids yield less soluble dyestuffs. Dyestuffs yielding blue shades are obtained with p-nitraniline derivatives as coupling components; thus the dyestulf from l-diazo- 4-11itrobenzene-Q-sulfonic acid and 3-amino- LS-naphthalene dicarboxyllc acid for in stance dyes wool violet tints fast to washing.

Ewample 2.

A solution of 3aminonaphthalenc-l.8-dicarboxylic acid is prepared according to the indications of Example 1 and this solution is treated with a diazo solution prepared from 11.7 parts of 5-nitro-2-amino-lhenol- 4-sulfonic acid. The dyestuif thus 0 tained is isolated by addition of common salt, tiltered and dried. It forms a brownish-black I powder, dissolving in water with violet-red,

in sulfuric acid with yellowish-brown coloration. tints, changing to yellowish-green and becoming fast, especially fast to potting, by after-treatment with chromium. When printed on cotton in presence of a chromium mordant it yields yellowish-green tints.

The new dyestuff' inform of its sodium salt corresponds most probably with the following formula:

(OONa ("OONu Analogous dycstulls are obtained with other ortho-annnophenols or ortho-aminophenol The new dyestufl' yields on wool red after-treatment with chromium.

V Emample 3. 10.6 parts of 3-aminonaphthalene-1.8-di

carboxylic acid anhydride are dissolved in' 150 parts of hot water by means of 10 parts of a caustic soda solution of 30 per cent stren th and treated after cooling at about 20 with 30 parts of ice and 25 parts of hydrochloric acid of 30 per cent strength. S-aminonaphthalene 1. 8- dicarboxylic acid separates which, after addition of 35 parts of nitrite, dissolves first and precipitates after a short time as diazo compound. The suspension thus obtained is poured into an alkaline solution of. 6.9 parts of salicylic acid; the coupling being achieved, the excess of alkali is neutralized with acid and the dyestuff. salted out, filtered and dried. It forms an easily soluble, yellow crystalline powder, dissolving in water with yellow, in sulfuric acid with orange-yellow coloration and yields on wool when dyed in an acid bath, yellow tints which become very fast, especially fast to potting by after-treatment with chromium. When printed with chroniiuni mordants the new dyestuif yields fast, pure yellow tints. The dyestufi' in form of its sodium salt corresponds most probably with the following formula:

COONa COONa COONa N N-'- OH Analogous dyestuffs are obtained with cresotinic acid; further yellow inordant dyestufis E mample 4.

10.6 parts of 3-amino-1.8-dicarboxylic acid anhydride are diazotized as indicated in the preceding example and the diazo suspension thus obtained is poured into an alkaline solution of 16 parts of 1.8-aminonaphthol- 4.6-disulfonic acid. Couipling occurs very rapidly and the dyestu isolated in the usual manner, forms a brown powder, dissolving in water and sulfuric acid with redviolet coloration. When dyed in an acid bath it yields on wool red-violet tints changing very little by after treatment with chromium. When printed in present of chromium mordants, it yields also red-violet tints.

The dyestutl' in form of its sodium salt corresponds most probably with the following formula:

COONQ COONB gig I on rye,

N=N t SOsNu SO;Na

arninonaphthols in middle position yield gray to black tints.

Thus the dyestutf obtained for example.

by coupling 3-amino1.8-naphthalene dicarboxylic acid with 1.8-aminonaphthol-4.6-disulfonic acid in an acid solution, corres 0nding in form of its sodium salt most pro ably with the following formula:

GOONa NE, on

SOaNs bOaNa yields violet-brown tints, where as the disazodyestuti' obtained by coupling in an alkaline solution the above named dyestufl with a second molecule of 3-diazo-1.8-naphthalenedicarboxylie acid and corresponding in form of its sodium salt most probably with the following formula:

CQONa COONa COONa COONB NH: OH

SIOQNE scam dissolves in water with blue coloration and yields on wool grayish-blue tints.

1,oe7,s1e a The following table shows some of the properties of the new dyestnfi's.

- .hrmue Coupling com- Dyestufl Solutionin Solution in Aciddyemg pyemg on 'w ponent. powder. i water. H 804 on wool. 82 ,333 zgt gg Aniline 3-eminonaphtha- 'BrownishiYellowish- Brownisli- Red Red lene-LS-dicarorange l red red boxylic acid o-toluidine Yellowisb- FYellow Red Orange rown o-sulianilic acid id. ReddisliiReddish- Yellowisli- Red Red Orange.

brown I yellow red l-amino-4-acetyl-mnino-benzolid. Bluishi id. Greemsh- Bluish-rcd Brown.

2-sulionic acid brown yellow a'-naphtl1ylaminc id. Reddish- Yellow Greenisli- Red Brown. brown i blue 4-chloro 5-sullo-2-amino-lid. Blackish- Yellowisli- Brown \ellowish- Yellowish- (Jlire.

p en a brown brown olive olive 5-nitrc-4-sullo-2-amino-lid. Brownisln Violet-red-.. Yellowish- Red Yellowish- Greenlanen black brown green gray.

4-chloro-6-niLro-2-annno-lid. Brown .4 Brownish- Reddlsh- Brown Olive (lray.

phenol i red brown 5-nitro-4-cl1loro-2-oinino-1- id. GreenishiRed-violot" Reddieli- Bluish-red.. Green Gray.

phenol bl ck brown 4-sulfo-2-amino-l-plienobfiid. Brown-red.. Bordeaux-.. Bordeaux... Yellowishlirown...... Brown.

carboxylic acid i Bordeaux -a -Phenol-(iid. B uish- Reddish- Violet Reddish- Violet- Brown.

carboxyllc acid brown brown brown brown 4-nitro-2-amino-l-phenolfiid. ReddishlBrownish- Red Bordeaux..- Bordeaux... id.

curboxylic acid brown yellow 4.6-diniiro-Z-amino-l-phenol... id. Greenishi Brownisli- Greenish- Greenish- Yrllow-olive ()live.

black 4 red yellow I brown G-nitro-Z-amino-l-phenoliid. Brown Reddislr Reddish Reddishid. carboxylic acid 5 brown brown brown 4-:nnino-1-hydroxybenzol-2- id. Reddisli- 're- Red Red Red-hrown.. Brown.

carboxylic acid brown i 4miLrO-I-BmlUO-Z-SUHOHl0DCNL. id, Blackisli- =Violet. Yellowisli- Violet Red-violet.

brown brown o-nitro-Z-enlino-l-phenol-iid. Black Violet-red Brownish- Gray.

sulfonic acid 5 yellow Zi-aminonaphthalene-LS- o-cresoiinic acid... Orange- Yellow Orange Reddish- Reddisli- Reddishdicarboxylic acid yellow yellow yellow yellow yellow. (l-aminonaphthalene-l.8- l-(-3' carboxyl)- Red Orange- Yellowid. ,Greenlshid.

dioarboxylic acid phenyl-fi-pyra- I yellow brown yellow zolone-iicarboxylic acid .id. fl-naphthol.. Brggnish- Red Bordeaux... Red Red Red.

, r id. ethyl-B-naphthyl- Red Yellowish- Blue Red.. Red Reddishamine red brown. B-mninonaphihalcne-LS- 2-naphthylmnine- Brown Yellowlsh- Bordeaux... Yellowish- Yellowisli- Yellowish dicnrboxylic acid (i-sulionic acid brown brown brown brown id. 1.8-arninonaphthol- Violet- Bordeaux-.. Bluish-red.- Reddish- Reddlsh- Violet.

. 4-sulionic acid brown violet violet (alkaline coupling) y y- Grayishid. Violet Bluisli-red.- Vio et Greenishnapnthalenednblack blue. disulionic acid id. ll-hydroxynaph- Black Red Bordeaux... BIOWlllSh- Brown Red.

thalene-LS- red dlcarboxylic acid.

'What'we claim is 1. As a new process the herein described oi' 3-amino-naphthalene-LS-dicaryl-didzo compounds of coupling hoxylic acid with or the benzene and naphthaleneseries.

2. As a new process the herein described coupling of 3znnino-nnphthalene-1.8-dicarhoxylic acid with 'nryLopounds of the benzene and naphthalene series.

3. As new presence of a 1.8naphthnlid acid complex.

coon

not containing any hydroixyl groups, which dyestufis form yellow to brown and black COOH iydroxydiazo coinproducts the herein described uzodlyestufis derived from domino-naphihnlene-l.H-dimu-boXyIic acid, the general formula, of which is characterized by the coon 000m wherein R means an aromatic residue, which 45 dyestufl's form yellow1sh-brown to black powders, dissolving in water with yellowishred to violet, in sulfuric acid with greenishyellow to brown, red, violet and green-blue coloration, dyeing wool in an acid bath yellow-red to reddish-brown and violet tints, and which by afterchroming are converted into greenish-yellow to red, brown, violet and green tints, yielding, when printed on cotton with chromium mordants, yellow to red, brown, violet, green and gray tints.

5. As new products the herein described new azo dyestutfs corresponding in form of their sodium salts with the general formula:

COON-u COONu wherein R means an aromatic residue carrying a hydroxyl group in ortho position to the azo-bridge, which products form reddish-brown to black powders, dissolving. in water with yellowish-brown to red, Violet and brown, in sulfuric acid with greenishyellow to red, violet and reddish-brown coloration, dyeing wool in an acid bath yellowish-olive to red, brown, violet and greenishbrown tints which are converted by afterchroming into yellowish-olive to red-brown,

' Bordeaux and green tints and yielding when printed on cotton with chromium mordants olive to greenish-gray, gray and brown tints.

'6. Material dyed and printed with the new dyestufl's of claim 8.

7. Material dyed and printed with the new dyestuffs of claim 4.

8. Material dyed and printed with the new dyestufi's of claim 5.

In witness whereof we have hereunto signed our names this 20th day of July MAX- ISLER. LUCAS VON MECIIEL. 

